Non-heme iron(IV)-oxo species can perform a variety of oxidation reactions in various mononuclear and dinuclear enzymatic systems. In the recent years, they have garnered a large amount of interest due to their potential to catalyze C-H bonds, specifically the sought-after conversion of methane to methanol. Various model compounds with S=2 spin have been synthesized allowing a much more detailed analysis of these high spin systems. It has been spectroscopically analyzed that there exist three pathways for the oxyl radical to form. There is one pathway through σ channel and two degenerate pathways through the π channel. The π channel can cause a self-oxidation of C-H bonds on the surrounding ligands of the complex. This distinction means in some cases it would be beneficial to prefer one channel over. Using multireference wave function theory, we can gain an understanding of the characteristics of these reaction channels and how different ligand fields affect them. Finding trends of reactivity and development of the oxyl character will allow the best optimization these systems and aid in the design of novel catalysts. Considering the reactivity of these channels using ligand fields of varying strength is one way of gaining information about the system. Use of specific ligands can aid or hinder reactivity through the two channels. We are offering new insight with the use of multi-reference methods at the CASSCF/CASPT2 level as well as an examination of an array of strong and weak field ligand systems.<br/>

Computational examination of the reaction channels of non-heme iron(IV)-oxo species

255th National Meeting (2018)

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